Agent and method for dyeing keratin fibers

ABSTRACT

The agent for dyeing keratin fibers contains one or more aryl and/or benzyl alcohols, one or more oxidizing enzymes, especially vanillyl oxidase, derivatives of vanillyl oxidase or galactose oxidase, and a nucleophilic compound that forms a dye for dyeing keratin fibers in the presence of the alcohols and enzymes. A method for dyeing keratin fibers with this agent is also disclosed. Two-component kits for performing the method of dyeing keratin fibers include a first compenent (A) and a second component (B) separate from the first component. The first component (A) includes the nucleophilic compound, the alcohol and optionally the oxidizing enzyme. The second component (B) includes the oxidizing enzyme when it is not included in the first component or more alcohol.

The present invention relates to an agent and to a method for dyeingkeratin fibers, especially human hair.

The reaction between ketones or aldehydes, especially aromatic aldehydessuch as benzaldehyde and various substituted benzaldehydes, withcompounds having an active CH group, water being split off and compoundsformed, which are suitable for dyeing keratin fibers, has already beendescribed earlier, for example, in the German Offenlegungsschrift 197 17281 and the German utility patent 299 08 464. The possibility ofsensitizing when the ketone or the aldehyde is applied directly on thehair or the scalp is a disadvantage of using this reaction betweenketones or aldehydes and compounds with active CH groups. Furthermore,it is difficult to incorporate especially aldehydes into the dyeingagents and to keep such agents for longer periods, since the aldehydestend to oxidize in air, forming carboxylic acids, which do notparticipate in the color-forming reaction.

The present application avoids the direct use of ketones or aldehydes byemploying primary or secondary alcohols as aldehyde or ketone precursorsfor the aforementioned reaction, the alcohols being oxidizedenzymatically in situ to the corresponding aldehydes or ketones.

The object of the present application therefore is an agent for dyeingkeratin fibers, especially wool, silk or hair, especially human hair,wherein at least one compound with a nucleophilic reaction center, atleast one alcohol from the group comprising aryl alcohol derivatives andbenzyl alcohol derivatives and at least one oxidizing enzyme iscontained.

As inventive alcohol, especially aryl alcohols or benzyl alcohols offormula (I) may be named, which can be converted by enzyme-catalyzedoxidation to the corresponding carbonyl compounds;

Ar—(CH═CH)_(n)—CH₂OH  (I)

in which n=0, 1 or 2;

and Ar is a group of formula

in which Y is an oxygen atom, a sulfur atom or an NR^(a) group; R1′,R2′, R3′, R4′, R5′, R6′ and R7′ independently of one another are ahydrogen atom, a hydroxy group, a methoxy group, an aryl group, ahalogen atom (F, Cl, Br, I), a —CHO— group, a —COR^(a) group, a—CO₂R^(a) group, an NO₂— group, an —OCOR^(a) group, an —OCH₂aryl group,an —NH₂ group, an —NH₃ ⁺ group, an —NHR^(a) group, an —NH₂R^(a+) group,an —N(R^(a))₂ group, an —N(R^(a))₃ ⁺ group, an —NHCOR^(a) group, an—NHCOOR^(a) group, in which R^(a) is a hydrogen atom, a linear orbranched C1 to C4 alkyl group, an optionally substituted, aromatic,carbocyclic group or heterocyclic group, or R4′ and R5′ together withthe carbon atom of the aromatic ring form a 5-membered or 6-memberedalicyclic or aromatic ring, which optionally may contain one or moresulfur, nitrogen or oxygen atoms.

The following compounds of formula (I) are particularly preferred:benzyl alcohol, 4-hydroxy-benzyl alcohol, 4-hydroxy-3-methoxy-benzylalcohol (vanillyl alcohol), 3-hydroxy-4-methoxy-benzyl alcohol(isovanillyl alcohol), 3,5-dimethoxy-4-hydroxybenzyl alcohol,3,4-dihydroxy-benzyl alcohol, 2-hydroxy-3-methoxy-benzyl alcohol,4-ethoxy-benzyl alcohol, 4-carboxy-benzyl alcohol, 2,5-dihydroxy-benzylalcohol, 2,4-dihydroxy-benzyl alcohol, 2-hydroxy-benzyl alcohol,3,5-dimethoxy-4-hydroxy-benzyl alcohol, 4-hydroxy-2-methoxy-benzylalcohol, 2,4-dimethoxy-benzyl alcohol, 2,3-dimethoxy-benzyl alcohol,2,5-dimethoxy-benzyl alcohol, 3,5-dimethoxy-benzyl alcohol,3,4-methylenedioxy-benzyl alcohol, 3,4-dimethoxy-benzyl alcohol,3-ethoxy-4-hydroxy-benzyl alcohol, 3,5-dimethyl-4-hydroxy-benzylalcohol, 3,4-dimethoxy-5-hydroxy-benzyl alcohol, 3,4,5-trimethoxy-benzylalcohol, 2,4,6-trihydroxy-benzyl alcohol, 3,4,5-trihydroxy-benzylalcohol, 2,3,4-trihydroxy-benzyl alcohol,3,5-di-t-butyl-4-hydroxy-benzyl alcohol, 2-nitro-benzyl alcohol,3-nitro-benzyl alcohol, 4-nitro-benzyl alcohol, 2-amino-benzyl alcohol,3-amino-benzyl alcohol, 3-amino-4-methyl-benzyl alcohol,3,5-diamino-benzyl alcohol, 4-amino-benzyl alcohol,4-dimethylamino-benzyl alcohol, 4-diethylamino-2-hydroxy-benzyl alcohol,4-diethylamino-3-methoxy-benzyl alcohol,4-dimethylamino-2-methoxy-benzyl alcohol, 4-dibutyl-amino-benzylalcohol, 3-methoxy-4-(1-pyrrolidinyl)-benzyl alcohol,(4-methoxy-naphthalene-1-yl)-methanol,(4-dimethylamino-naphthalene-1-yl)-methanol,2-(hydroxymethyl)-1-naphthol, 1-naphthalene-methanol,2-naphthalene-methanol, (2-methoxy-naphthalene-1-yl)-methanol,4-hydroxy-methyl-naphthalene-1-ol, 4′-hydroxymethyl-biphenyl-4-ol,(4-hydroxymethylphenyl)-methanol,4-(3-hydroxy-propenyl)-2-methoxy-phenol,4-(3-hydroxy-propenyl)-2,6-dimethoxy-phenol,3-(4-dimethylaminophenyl)-prop-2-ene-1-ol,5-(4-(diethylamino-phenyl)-penta-2,4-diene-1-ol,thiophene-2-yl-methanol, (5-hydroxymethyl-thiophene-2-yl)-methanol,thiophene-3-yl-methanol, (1H-pyrrole-2-yl)-methanol,(1-methyl-1H-pyrrole-2-yl)-methanol, (5-methyl-furan-2-yl)-methanol,(1H-indole-3-yl)-methanol, and (6-methyl-1H-indole-3-yl)-methanol.

The use of the alcohol instead of the corresponding carbonyl compound ofthe present invention makes a rapid intensive dyeing of the fibers,especially of the keratin fibers possible in the presence of a compoundwith a nucleophilic center with the addition of an oxidizing enzyme. “Anoxidizing enzyme” is understood here to be an enzyme, which is able tocatalyze the oxidation of the alcohol to an aldehyde or ketone. Thefollowing are named as examples of such enzymes, which are, however, notlimited to these: alcohol dehydrogenases (E.C. Classification 1.1.1.-),alcohol oxidases (E.C. Classification 1.1.2- and 1.1.3- and 1.1.99-),flavinoxidases (E.C. Classification 1.2.--), laccases (E.C.Classification 1.4.---), peroxidases (E.C. Classification 1.11.1.-),hydroxylases and monooxygenases (E.C. Classification 1.13.12- and1.13.99-).

The enzyme is used preferably in an amount of 5 to 100 units permillimole of substrate (alcohol). A unit of enzyme activity refers hereto the amount of enzyme, which is required to catalyze the oxidation of1 micromole of alcohol per minute.

“Compounds with a nucleophilic reaction center” are understood to becompounds, which are able to form unsaturated carbon-carbon orcarbon-nitrogen bonds by reaction with the electrophilic carbonyl carbonof the aldehyde or ketone. Suitable compounds with a nucleophilicreaction center of the present invention are, for example, primary orsecondary aliphatic or aromatic amines, nitrogen-containing heterocycliccompounds, amino acids, oligopeptides with 2 to 9 amino acid groups,aromatic hydroxy compounds and compounds with active CH group.

Suitable compounds with primary or secondary amino groups are, forexample, primary aromatic amines such asN,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine,N-(2-hydroxyethyl)-N-ethyl-p-phenylenediamine,N,N-bis-(2-hydroxyethyl)-p-phenylenediamine,N-(2-methoxyethyl)-p-phenylenediamine, 2,3-dichloro-p-phenylenediamine,2,4-dichloro-p-phenylenediamine, 2,5-dichloro-p-phenylenediamine,2-chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoanilinedihydrobromide, 2-aminophenol, 3-aminophenol, 4-aminophenol,2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol,o-phenylenediamine, m-phenylenediamine, p-phenylenediamine,o-toluylenediamine, m-toluylenediamine, 2,5-diaminotoluene,2,5-diaminophenol, 2,5-diaminophenethol, 4-amino-3-methylphenol,2,4-diaminophenoxyethanol, 2-(2,5-diamino-phenyl)-ethanol,2-(2,5-diaminophenoxy)-ethanol, 4-methylaminoaniline,3-amino-(2-hydroxyethyloxy)aniline, 3,4-methylenediaminoaniline,3,4-methylenedioxyaniline, 3-amino-2,4-dichloro-phenol,4-methylamino-phenol, 2-methyl-5-amino-phenol, 3-methyl-4-amino-phenol,2-methyl-5-(2-hydroxyethylamino)-phenol,6-methyl-3-amino-2-chloro-phenol, 2-methyl-5-amino-4-chloro-phenol,5-(2-hydroxyethylamino)-4-methoxy-2-methyl-phenol,1,3-diamino-2,4-dimethoxybenzene, 2-aminobenzoic acid, 3-aminobenzoicacid, 4-aminobenzoic acid, 2,3-diaminobenzoic acid, 2,4-diaminobenzoicacid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid,3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4-aminosalicylic acid,5-amino-salicylic acid, 3-amino-4-hydroxy-benzoic acid,4-amino-3-hydroxy-benzoic acid, 2-aminobenzenesulfonic acid,3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid,3-amino-4-hydroxybenzenesulfonic acid,4-amino-3-hydroxynaphthalene-1-sulfonic acid,6-amino-7-hydroxy-naphthalene-2-sulfonic acid,7-amino-4-hydroxynaphthalene-2-sulfonic acid,4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoicacid, 3-aminophthalic acid, 5-aminoisophthalic acid,1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 1,2,4,5-tetraaminobenzene,2,4,5-triaminophenol, pentaaminobenzene, hexaminobenzene,2,4,6-triaminoresorcinol, 4,5-diaminopyrocatechol,4,6-diaminopyrogallol, 3,5-diamino-4-hydroxypyrocatechol, aromaticanilines or phenols with a further aromatic group, such as4,4′-diaminostilbene, 4,4′-diaminostilbene-2,2′-disulfonic acidmonosodium salt or 4,4′-diaminostilbene-2,2′-disulfonic acid disodiumsalt, 4,4-diamino-diphenylmethane, 4,4-diaminodiphenylsulfide,4,4-diaminodiphenylsulfoxide, 4,4-diaminodiphenylamine,4,4-diaminodiphenylamine-2-sulfonic acid, 4,4′-diaminiobenzophenone,4,4′-diamininobenzophenone diphenyl ether,3,3′,4,4′-tetraaminodiphenyl), 3,3′,4,4′-tetraamino-benzophenone,1,3-bis-(2,4-diaminophenoxy)-propane,1,8-bis-(2,5-diaminophenoxy)-3,6-dioxaoctane,1,3-bis-(4-aminophenylamino)-propane,1,3-bis-(4-amino-phenylamino)-2-propanol,1,3-bis-[N-(4-aminophenyl)-2-hydroxyethyl-amino]-2-propanol, N,N-bis-[2,(4-aminophenoxy)-ethyl]-methylamine and N-phenyl-1,4-phenylenediamine.

Suitable nitrogen-containing heterocyclic compounds are, for example,2-aminopyridine, 3-aminopyridine, 4-aminopyridine,2-amino-3-hydroxy-pyridine, 2,6-diaminopyridine, 2,5-diaminopyridine,2,3-diaminopyridine, 2-dimethylamino-5-aminopyridine,2-methylamino-3-amino-6-methoxy-pyridine, 2,3-diamino-6-methoxypyridine,2,6-dimethoxy-3,5-diaminopyridine, 2,4,5-triaminopyridine,2,6-dihydroxy-3,4-dimethylpyridine,2,4-dihydroxy-5,6-diamino-pyrimidine, 4,5-triamino-pyrimidine,4-hydroxy-2,5,6-triamino-pyrimidine,2-hydroxy-4,5,6-triamino-pyrimidine, 2,4,5,6-tetraamino-pyrimidine,2-methylamino-4,5,6-triamino-pyrimidine, 2,4-diamino-pyrimidine,4,5-diamino-pyrimidine, 2-amino-4-methoxy-6-methyl-pyrimidine,3,5-diaminopyrazole, 3,5-diamino-1,2,4-triazole, 3-aminopyrazole,3-amino-5-hydroxypyrazole, 2-aminoquinoline, 3-aminoquinoline,8-aminoquinoline, 4-aminoquinaldine, 2-aminonicotinic acid,6-aminonicotinic acid, 5-amino-isoquinoline, 5-aminoindazole,6-aminoindazole, 5-aminobenzimidazole, 7-aminobenzimidazole,7-amino-benzothiazole, 5-amino-benzothiazole,2,5-dihydroxy-4-morpholinoaniline as well as indole and indolinderivatives, such as 4-aminoindole, 5-aminoindole, 6-aminoindole,7-aminoindole, 5,6-dihydroxyindole, 5,6-dihydroxyindoline and4-hydroxyindoline.

The aforementioned amines and heterocyclic compounds can be used in freeform as well as in the form of the physiologically tolerated salts, suchas salts of inorganic acids like hydrochloric acid or sulfuric acid.

All naturally occurring and synthetic amino acids, such as arginine,histidine, tyrosine, phenylalalanine, dihydroxyphenylalanine, ornithine,lysine and tryptophane come into consideration as amino acids.

As oligopeptides, all naturally occurring or synthetic oligopeptides, aswell as the oligopeptides contained in polypeptide or proteinhydrolysates, can be used, provided that they are sufficiently solublefor use in the inventive dyeing agents. Glutathione or theoligopeptides, contained in the hydrolysates of collagen, keratin,casein, elastin, soybean protein, wheat gluten or almond protein, arenamed as examples. In this connection, the joint use of theoligopeptides with compounds with a primary or a secondary amino groupor with aromatic hydroxy compounds is preferred.

Suitable aromatic hydroxy compounds are, for example,2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol,2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol,hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone,2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol,3-dimethylaminophenol, 2-(2-hydroxyethyl)-phenol,3,4-methylenedioxyphenol, 2,4-dihydroxybenzoic acid,3,4-dihydroxy-benzoic acid, 2,4-dihydroxy-phenylacetic acid,3,4-dihydroxyphenylacetic acid, gallic acid, 2,4,6-trihydroxybenzoicacid, 2,4,6-trihydroxy-acetophenone, 2-chlororesorcinol,4-chlororesorcinol, 1-naphthol, 1,5-dihydroxynaphthalene,2,3-dihydroxy-naphthalene, 2,7-dihydroxynaphthalene,4-hydroxy-2-naphthalene sulfonic acid and 3,6-dihydroxy-2,7-naphthalenesulfonic acid.

As suitable compounds with an active CH group,1,2,3,5-tetramethyl-3H-indolium iodide, 1,2,3,5-tetramethyl-3H-indoliummethosulfate, 2,3-dimethyl-benzothiazolium iodide,2,3-dimethyl-benzothiazolium-p-toluenesulfonate, rhodanine,rhodanine-3-acetic acid, 1-ethyl-2-quinaldinium iodide,1-methyl-2-quinaldinium iodide, barbituric acid, thiobarbituric acid,1,3-dimethyl-thiobarbituric acid, 1,3-diethyl-thiobarbituric acid,oxindole, 3-indoxyl acetate, cumaranone,1-methyl-3-phenyl-2-pyrazolinone and enamines of Formula (II) or theirsalts of Formula (IIa),

in which R1 is a single ring or multi-ring aromatic group, especially a5-membered or 6-membered aryl group (preferably a phenyl group), whichoptionally is substituted by a C1 to C4 alkyl group, a C1 to C4hydroxyalkyl group, a hydroxy group, a methoxy group, a dialkylaminogroup or a halogen group (F, Ck, Br, I), a 5-membered or 6-memberedhetero cyclic ring (preferably a pyridyl group or a naphthyl group),which optionally is substituted by a C1 to C4 alkyl group, a C1 to C4hydroxyalkyl group, a hydroxy group, a methoxy group, a dialkylaminogroup or a halogen group (F, Cl, Br, I); R2 is a linear or branched C1to C8 alkyl group, a linear or branched C1 to C8 hydroxyalkyl group or aC1 to C8 alkoyalkyl group, possibly with oxygen atoms between the carbonatoms of the alkyl chain; R3 is a linear or branched C1 to C8 alkylgroup, a C1 to C8 alkoxyalkyl group, a linear or branched C1 to C8alkylene group, a C1 to C8 alkoxy alkylene group, an oxygen atom, asulfur atom, an —NH group or an —NR group, in which R is an alkyl group,an alkoxyalkyl group, a hydroxyalkyl group or hydrogen, a cycliccompound possibly being formed by the R1 and R3 groups together with thenitrogen atom and the carbon atom of the basic enamine structure, and R4is hydrogen, a linear C1 to C4 alkyl group or a branched C1 to C4 alkylgroup and A⁻ is the anion of an organic or inorganic acid.

Especially preferred compounds with a nucleophilic reaction center arethe following enamines of Formulas (III) to (X), in which X is a carbonatom with two C1 to C4 alkyl groups, which may be the same or different(especially 2 methyl groups), a carbon atom, substituted by a C1 to C4alkyl group, and a carbon atom, substituted by a hydroxy group, a sulfuratom, an alkylated nitrogen atom, a not alkylated nitrogen atom or anoxygen atom; and R2 is a linear or branched C1 to C8 alkyl group, alinear or branched C1 to C8 hydroxyalkyl group or a C1 to C8 alkoxyalkylgroup, oxygen atoms possibly being present between the carbon atoms ofthe alkyl chain; R4 is hydrogen, a linear C1 to C4 alkyl group or abranched C1 to C4 group; R5, R6, R7 and R8 independently of one anotherare hydrogen, a linear or branched C1 to C4 alkyl group, a linear orbranched C1 to C4 hydroxyalkyl group, a hydroxy group, a methoxy group,an amino group, a mono(C1 to C4) alkylamino group, a di(C1 to C4)alkylamino group, a benzyl group or a halogen atom (F, Cl, Br, I); andA⁻ is chloride, bromide, iodide, sulfate, hydrogen sulfate,toluenesulfonate, benzenesulfonate, monomethyl sulfate,hexafluorophosphate, hexafluoroantimonate, tetrafluoroborate,tetraphenylborate, formate, acetate or propionate, the chloride ion,tetrafluoroborate ion, the acetate ion and the hydrogen sulfate ionbeing particularly preferred.

The following compounds with nucleophilic reaction centers arepreferred: 1,3,3-trimethyl-2-methylene-indoline as well as its salts,

1,3,3,4-tetramethyl-2-methylene-indoline as well as its salts,

1,3,3,5-tetramethyl-2-methylene-indoline as well as its salts,

1,3,3,6-tetramethyl-2-methylene-indoline as well as its salts,

1,3,3,7-tetramethyl-2-methylene-indoline as well as its salts,

1,3,3,6,7-pentamethyl-2-methylene-indoline as well as its salts,

1,3,3,5,7-pentamethyl-2-methylene-indoline as well as its salts,

1,3,3,4,7-pentamethyl-2-methylene-indoline as well as its salts,

5-chloro-1,3,3-trimethyl-2-methylene-indoline as well as its salts,

5-fluoro-1,3,3-trimethyl-2-methylene-indoline as well as its salts,

5-isopropyl-1,3,3-trimethyl-2-methylene-indoline as well as its salts,

5-hydroxy-1,3,3-trimethyl-2-methylene-indoline as well as its salts,

5-methoxy-1,3,3-trimethyl-2-methylene-indoline as well as its salts,

5-amino-1,3,3-trimethyl-2-methylene-indoline as well as its salts,

5-nitro-1,3,3-trimethyl-2-methylene-indoline as well as its salts,

5-N-acetylamino-1,3,3-trimethyl-2-methylene-indoline as well as itssalts,

6-hydroxy-1,3,3-trimethyl-2-methylene-indoline as well as its salts,

6-methoxy-1,3,3-trimethyl-2-methylene-indoline as well as its salts,

5-methoxy-6-nitro-1,3,3-trimethyl-2-methylene-indoline as well as itssalts,

5-methoxy-6-N-acetylamino-1,3,3-trimethyl-2-methylene-indoline as wellas its salts,

5-methoxy-6-amino-1,3,3-trimethyl-2-methylene-indoline as well as itssalts,

5,6-methylenedioxy-1,3,3-trimethyl-2-methylene-indoline as well as itssalts,

5,6-dihydroxy-1,3,3-trimethyl-2-methylene-indoline as well as its salts,

5,6-dimethoxy-1,3,3-trimethyl-2-methylene-indoline as well as its salts,

4,5-dihydroxy-1,3,3-trimethyl-2-methylene-indoline as well as its salts,

5,7-dihydroxy-1,3,3-trimethyl-2-methylene-indoline as well as its salts,

5-amino-6-methoxy-1,3,3-trimethyl-2-methylene-indoline as well as itssalts,

5-amino-7-hydroxy-1,3,3-trimethyl-2-methylene-indoline as well as itssalts,

5-hydroxy-7-amino-1,3,3-trimethyl-2-methylene-indoline as well as itssalts,

5-hydroxy-7-N-acetylamino-1,3,3-trimethyl-2-methylene-indoline as wellas its salts,

1-methyl-3-spiro-cyclopropyl-2-methylene-indoline as well as its salts,

1-methyl-3-spiro-cyclohexyl-2-methylene-indoline as well as its salts,

1-methyl-3-spiro-cyclohexyl-5-hydroxy-2-methylene-indoline as well asits salts,

1-methyl-3-spirocyclohexyl-5-methoxy-2-methylene-indoline as well as itssalts,

1-(2′-hydroxyethyl)-3,3-dimethyl-2-methylene-indoline as well as itssalts,

1,3,3-trimethyl-2-methylene-3H-benz[e]indole as well as its salts andN-ethyl-2-methylene-benzthiazole as well as its salts; the5-nitro-1,3,3-trimethyl-2-methylene-indoline,5-methoxy-6-nitro-1,2,3,3-tetramethyl-3H-indolium-chloride,5-N-acetylamino-1,2,3,3-tetramethyl-3H-indolium acetate,1,3,3-trimethyl-2-methylene-indoline, 1,2,3,3-tetramethyl-3H-indoliumchloride, 1,2,3,3-tetramethyl-3H-indolium bromide,1,2,3,3-tetramethyl-3H-indolium iodide, 1,2,3,3-tetramethyl-3H-indoliumsulfate, 1,2,3,3-tetramethyl-3H-indolium-hydrogen sulfate,1,2,3,3-tetramethyl-3H-indolium methyl sulfate,1,2,3,3-tetramethyl-3H-indolium hexafluorophosphate,1,2,3,3-tetramethyl-3H-indolium hexafluoro antimonate,1,2,3,3-tetramethyl-3H-indolium tetrafluoroborate,1,2,3,3,5-pentamethyl-3H-indolium iodide,1,2,3,3,7-pentamethyl-3H-indolium tetrafluoroborate,1,2,3,3,6,7-hexamethyl-3H-indolium tetrafluoroborate,1,2,3,3,5,7-hexamethyl-3H-indolium tetrafluoroborate,1,2,3,3,4,7-hexamethyl-3H-indolium tetrafluoroborate,5-chloro-1,2,3,3-tetramethyl-3H-indolium iodide,5-fluoro-1,2,3,3-tetramethyl-3H-indolium iodide,5-isopropyl-1,2,3,3-tetramethyl-3H-indolium iodide,5-methoxy-1,2,3,3-tetramethyl-3H-indolium iodide,5-hydroxy-1,2,3,3-tetramethyl-3H-indolium iodide,1,2,3,3-tetramethyl-3H-benz[e]indolium chloride,1,2,3,3-tetramethyl-3H-benz[e]indolium bromide,1,2,3,3-tetramethyl-3H-benz[e]indolium iodide,1,2,3,3-tetramethyl-3H-benz[e]indolium sulfate,1,2,3,3-tetramethyl-3H-benz[e]indolium hexafluorophosphate,1,2,3,3-tetramethyl-3H-benz[e]indolium methyl sulfate,1,2,3,3-tetramethyl-3H-benz[e]indolium hexafluoro antimonate,1,2,3,3-tetramethyl-3H-benz[e]indolium tetrafluoroborate,1,2-dimethyl-benzthiazolium iodide,5-methoxy-6-N-acetylamino-1,2,3,3-tetramethyl-3H-indolium acetate,5-hydroxy-6-N-acetylamino-1,2,3,3-tetramethyl-3H-indolium acetate andN-ethyl-2-methylbenzthiazolium iodide being especially preferred.

The alcohol and the compound with a nucleophilic reaction center areused in each case in a total amount of about 0.05 to 25% by weight andpreferably of 0.2 to 15% by weight, based on the ready-for-use agent.

As already mentioned above, alcohol dehydrogenases, alcohol oxidases,various flavin oxidases, laccases, peroxidases or similar enzymes can beused as oxidizing enzymes pursuant to the present invention. In apreferred embodiment of the invention, alcohol dehydrogenase asoxidizing enzyme, the oxidation being carried out in the presence of asuitable co-factor, such as the nicotinamide co-factor.

As “nicotinamide co-factor” NAD+, NADP+ and a variety of derivatives,which affect the enzymatic oxidation of alcohol to aldehydeadvantageously, can be used, for example. Such co-factors and theirderivatives are known to those skilled in the art. These co-factors canbe used in an amount approximately equimolar to the amount of alcoholor, if desired, the co-factor can be recovered. A plurality of methodsfor recovering the co-factor has become known from the art and any ofthese known methods can be used in the present invention. Suitablemethods for recovering the co-factor are described, for example, in G.L. Lemiere, J. A. Lepoivre, and F. C. Aldenweireldt, TetrahedronLetters, 26, 4257 (1985); in “Enzymes as Catalysts for OrganicSynthesis,” pp. 19-34, M. Schneider, Ed., Reidel Dordecht, 1986; Z.Shaked and G. M. Whitesides, J. Am. Chem. Soc. 102, 7104-5 (1980); J. B.Jones and T. Takamura, Can. J. Chem. 62, 77 (1984). In PreparativeBiotransformations (S. M. Roberts, editor), Chapter 3, pages3.1.1-3.1.6, John Wiley & Sons, Chichester, U.K. (1997), a recoverymethod is described, for which flavin mononeucleotides (FMN) are used,which transfer electrons to the oxygen, which functions as the ultimateoxidizing agent. For this method, 0.0005 to 0.05 moles of NAD+ or NADP+are used per mole of diol, which is to be oxidized. This represents arecovery factor for a co-factor of about 20 to 2000.

In a further preferred embodiment of the present invention, flavinoxidase, which catalyses the oxidation of alcohol to aldehyde usingmolecular oxygen as oxidant, is used as oxidizing enzyme. The use ofgalactose oxidase as oxidizing enzyme is particularly preferred.Likewise, the use of vanillyl alcohol oxidase as oxidizing enzyme isparticularly preferred. The use of derivative of the galactose oxidaseor of the vanillyl alcohol oxidase is also particularly preferred. A“derivative” is understood here to be an enzyme variant, which isobtained by a mutagenesis of the original enzyme by means of knownmethods. Examples of such mutagenesis are selective evolution, DNAshuffling, molecular breeding, gene rearrangement and recombination,random mutation, point mutation, gene site saturation mutagenesis, etc.Such methods are also known from the art, for example, from U.S. Pat.Nos. 5,605,793, 5,811,238, 5,830,721, 5,837,458, 5,965,408, 5,958,672and 6,001,574. Gene encoding derivatives, if desired, can be plannedand/or produced by inserting preferred codons.

Furthermore, compounds from the group of direct dyes, such as aromaticnitro dyes, azo dyes, anthraquinone dyes or triphenylmethane dyes, canbe added alone or in admixture with one another to optimize the dyeingresult and to produce special color effects.

Examples of nitro dyes are picramic acid,4-(2′,3′-dihydroxypropyl)-amino-3-nitro-trifluoro-methylbenzene,4,N-ethyl-N-(2′-hydroxyethyl)-amino-1-(2′-hydroxyethyl)-amino-2-nitrobenzene,2-chloro-6-ethylamino-4-nitrophenol,1-hydroxy-2-β-hydroxy-ethylamino-4,6-dinitrobenzene,4-(2′-hydroxyethyl)-amino-3-nitrochlorobenzene,2-amino-6-chloro-4-nitrophenol and4-(2′-hydroxyethyl)amino-3-nitro-methylbenzene.

Examples of azo dyes are1-(2′-methoxyphenylazo)-2-hydroxy-7-trimethyl-ammonium-naphthalene(Basic Red 76),4-(4′-sulfo-1-phenylazo)-1-(4″-sulfophenyl)-3-carboxy-5-hydroxypyrazolone(Acid Yellow 23), 4-amino-4′-bis[2″-hydroxyethyl]-amino-azobenzene(Disperse Black 9) and1-(4′-aminophenylazo)-2-hydroxy-7-trimethyl-ammonium naphthalene (BasicBrown 16).

Examples of anthraquinone dyes are1-methylamino-4-(2′-hydroxyethyl)amino-anthraquinone (Disperse Blue 3),1-amino-4-hydroxy-anthraquinone (Disperse Red 15),2-methoxy-1,4-diamino-anthraquinone (Disperse Red 11),1,4-diamino-anthraquinone (Disperse Violet 1),1-amino-4-methylamino-anthraquinone (Disperse Violet 4),1,4-bis(2′,3′-dihydroxypropyl)amino-anthraquinone,1-methylamino-4-(amino-n-propyltrimethyl-ammonium)-anthraquinone (BasicBlue 22), 1,4-bis-(2-hydroxyethyl)amino-5,8-dihydroxy-anthraquinone(Disperse Blue 7) and 1-methylamino-4-aminopropylamino-anthraquinone (HCBlue 8).

Examples of triphenylmethane dyes are[4-[[4-diethylamino]phenyl]-[4-(ethylamino)-1-naphthalinyl]methylene]-2,5-cyclohexadiene-1-ylidene]-N-ethyl-ethanamine(Basic Blue 7) and 4′,4′,4″-triamino-3-methyltriphenyl-carbeniumchloride (Basic Violet 14, Fuchsin AN).

The amount of direct dyes added preferably is 0.01% to 5% by weight andespecially 0.1% to 4% by weight.

The inventive agent represents a mixture of the components with theadditives, which are customary for such preparation.

Conventional, cosmetic additives, are, for example, solvents such aswater, low molecular weight, aliphatic, monohydric or multihydricalcohols, their esters and ethers, such as alkanols, especially with 1to 4 carbon atoms in the alkyl chain, such as ethanol, n-propanol ori-propanol, butanol, i-butanol, dihydric or trihydric alcohols,especially those with 2 to 6 carbon atoms, such as ethylene glycol,propylene glycol, 1,3-dihydroxypropane, 1,4-dihydroxybutane1,5-dihydroxypentane, 1,6-dihydroxyhexane, 1,2,6-trihydroxyhexane,glycerin, diethylene glycol, dipropylene glycol, polyalkylene glycols,such as triethylene glycol, polyethylene glycol, tripropylene glycol andpolypropylene glycol, lower molecular weight alkyl ethers ofmultihydric-alcohols, such as ethylene glycol monomethyl ether, ethyleneglycol monoethyl ether, ethylene glycol monopropyl ether, ethyleneglycol monobutyl ether, diethylene glycol monomethyl ether or diethyleneglycol monoethyl ether, triethylene glycol monomethyl ether, triethyleneglycol monoethyl ether, ketones and ketoalcohols, especially those with3 to 7 carbon atoms in the molecule, such as acetone, methyl ethylketone, diethyl ketone, methyl isobutyl ketone, methyl phenyl ketone,cyclopentanone, cyclohexanone and diacetone alcohol, ethers, such asdibutyl ether, tetrahydrofuran, dioxane or diisopropyl ether esters,such as ethyl formate, methyl formate, methyl acetate, ethyl acetate,propyl acetate, butyl acetate, phenyl acetate, ethylene glycol monoethylether acetate or hydroxyethyl acetate, amides, such asdimethylformamide, dimethylacetamide or N-methyl-pyrrolidone; as well asurea, tetramethylurea and thiodiglycol, furthermore wetting agents oremulsifiers from the classes of anionic, cationic, amphoteric, nonionicor zwitterionic, surface active substances, such as fatty alcoholsulfates, alkylsulfonates, alkylbenzenesulfonates,alkyltrimethylammonium salts, alkylbetaines, α-olefinsulfonates,ethoxylated fatty alcohols, ethoxylated nonylphenols, fatty acidalkanolamines, ethoxylated fatty acid ester, fatty alcohol polyglycolether sulfates, alkyl polyglucosides, thickening agents, such as highermolecular weight fatty alcohols, starch, cellulose derivatives,Vaseline, paraffin oil, fatty acids and other fat components inemulsified form, water-soluble, polymeric thickening agents, such asnatural gums, guar gum, xanthan gum, carob seed flour, pectin, dextran,agar-agar, amyloses, amylopectin, dextrins, clays or fully synthetichydrocolloids, such as polyvinyl alcohol, moreover, cosmetics such aslanolin derivatives, cholesterol, pantothenic acid, water solublecationic polymers, protein derivatives, pro-vitamins, vitamins, plantextracts, sugar and betaine, auxiliary materials, such as electrolytes,antioxidants, fatty amides, sequestering agents, film-forming agents,and preservatives.

The constituents mentioned are used in amounts customary for suchpurposes. For example, the wetting agents and emulsifiers are used inconcentrations of about 0.5 to 30% by weight, the thickeners in anamount of 0.1 to 25% by weight and the cosmetics in a concentration ofabout 0.1 to 5.0% by weight.

Normally, the individual constituents of the inventive dyeing agentsmust be stored separately from one another and are mixed togetherimmediately before use. The inventive agents can be produced in variousways. For example, the agents may be in the form of a 2-component kit,which consists of a component (A) containing the compound with anucleophilic reaction center, the alcohol, optionally the nicotinamideco-factor and/or the buffer, and a component (B), containing theoxidizing enzyme as well as optionally the nicotinamide co-factor and/orthe buffer. In a further, preferred, embodiment, the 2-component kitconsists of a component (A), containing the compound with a nucleophilicreaction center, the alcohol and the oxidizing enzyme, as well as,optionally, the nicotinamide co-factor and/or the buffer, and acomponent (B), containing the alcohol, as well as, optionally, thenicotinamide co-factor and/or the buffer. Preferably, components (A)and/or (B) are anhydrous, that is, they contain not more than 1% byweight of water, and are mixed with water, which may contain additional,conventional cosmetic additives, only before use.

The constituents of the inventive dyeing agent, that is, the alcohol,the compound with a nucleophilic carbon and the oxidizing enzyme, aswell as, optionally, the nicotinamide co-factor and/or the buffer, canalso be packed together, provided that they are anhydrous, that is,provided that they do not contain more than 1% by weight of water, andare mixed with water, which may contain additional conventional cosmeticadditives, only before use.

It is also possible to package the co-factor and the buffer separatelyand to mix them before use with the remaining components of the agent(3- or 4-component kit).

The dyeing of keratin fibers is usually carried out in an aqueousmedium. Mixtures, which contain at least 60% by weight of water and morepreferably at least about 70% by weight of water are regarded as“aqueous media”.

The pH of the ready-for-use dyeing agent is about 2 to 12, preferablyabout 4 to 10 and particularly about 6 to 9.

The individual components are mixed together before use and theready-for-use agent, so obtained, is then applied on the keratin fibers,which are to be dyed, water or an aqueous preparation, containing theusual cosmetic additives, optionally being added. The mixture is left onthe fibers, for example, on hair, for about 10 to 45 minutes andpreferably for about 30 to 40 minutes at about 10° to 70° C. andpreferably at about 15° to 50° C., after which the fibers are rinsedwith water and dried.

Dyeings with outstanding fastness properties, especially with respect tolight fastness, wash fasteners and rubbing fastness, especially on hair,are made possible by the inventive dyeing agents and dyeing method.

The object of the invention is described in greater detail by thefollowing examples, without being limited to these

EXAMPLES Examples 1 to 8

Use of Galactose Oxidase for Dyeing Hair in the Presence of1,2,3,3-tetramethyl-3H-indolium Hydrogen Sulfate and Substituted BenzylAlcohols

Galactose oxidase, as a lyophilized powder, the appropriatelysubstituted benzyl alcohol of Table 1, as well as1,2,3,3-tetramethyl-3H-indolium hydrogen sulfate are mixed together in a50 mL centrifuge tube, the mixture of the aforementioned componentsbeing diluted with water to a total volume of about 30 mL.

The hair was treated for 40 minutes at 37° C. with the dyeing solutionsof Table 1. Enzyme (galactose oxidase) was present in Examples 1 to 4and absent in Examples 5 to 8 (=control group). Subsequently the hairwas washed with water and dried. The dyeing results are summarized inTable 2.

TABLE 1 Potassium Alcohol (250 1,2,3,3- phosphate mmoles/L tetramethyl-buffer (250 stock 3H-indolium mmoles/L Example solution in Galactosehydrogen- stock No. DMSO oxidase sulfate solution) H₂O 1 Vanillyl 30 mg80 mg 6 mL 22.8 mL alcohol: 1.2 (200 units) (final (final mLconcentration: concentration: (final 10 mmoles/L) 100 concentration:mmoles/L) 10 mmoles/L) 2 Isovanillyl 30 mg 80 mg 6 mL 22.8 mL alcohol:(200 units) (final (final 1.2 mL concentration: concentration: (final 10mmoles/L) 100 concentration: mmoles/L) 10 mmoles/L) 3 p-hydroxy- 30 mg80 mg 6 mL 22.8 mL benzyl (200 units) (final (final alcohol:concentration: concentration: 1.2 mL 10 mmoles/L) 100 (final mmoles/L)concentration 10 mmoles/L) 4 p-amino- 30 mg 80 mg 6 mL 22.8 mL benzyl(200 units) (final (final alcohol: concentration: concentration: 1.2 mL10 mmoles/L) 100 (final mmoles/L) concentration: 10 mmoles/L) 5 Vanillyl— 80 mg 6 mL 22.8 mL alcohol: (final (final 1.2 mL concentration:concentration: (final 10 mmoles/L) 100 concentration: mmoles/L) 10mmoles/L) 6 Isovanillyl — 80 mg 6 mL 22.8 mL alcohol: (final (final 1.2mL concentration: concentration: (final 10 mmoles/L) 100 concentration:mmoles/L) 10 mmoles/L) 7 p-hydroxy- — 80 mg 6 mL 22.8 mL benzyl (final(final alcohol: concentration: concentration: 1.2 mL 10 mmoles/L) 100(final mmoles/L) concentration: 10 mmoles/L) 8 p-amino- — 80 mg 6 mL22.8 mL benzyl (final (final alcohol: concentration: concentration: 1.2mL 10 mmoles/L) 100 (final mmoles/L) concentration: 10 mmoles/L)

TABLE 2 Example No. Color Result 1 red 2 yellow-orange 3 orange 4intense pink 5 weak pink 6 weak pink 7 weak pink 8 weak pink

Examples 1 to 4 resulted in intensive colors. On the other hand,comparison Examples 5 to 8, which did not contain any galactose oxidase,resulted only in a weak coloration

Example 9

The Use of Horse Liver Alcohol Dehydrogenase for the in Situ Oxidationof Substituted Benzyl Alcohols in the Presence of1,2,3,3-tetramethyl-3H-indolium Hydrogen Sulfate.

The horse liver alcohol dehydrogenase-catalyzed oxidation of benzylalcohol in the presence of 1,2,3,3-tetramethyl-3H-indolium hydrogensulfate was carried out in a potassium phosphate buffer system (100mmoles per liter; pH=7) as follows. Solutions containing 2 to 15 mmolesper liter of 1,2,3,3-tetramethyl-3H-indolium hydrogen sulfate wereprepared. Subsequently, equimolar amounts of 2 mmoles/L solutions,containing the appropriate benzyl alcohol, were added and the totalvolume was made up to 1 mL with buffer solution. Thereupon, 0.25 mm ofoxidized nicotinamide co-factor (NAD+), as well as 10 units of horseliver alcohol dehydrogenase were added. The color development reactionwas observed at room temperature as a function of reaction time. After aperiod of observation of not more than 1 hour, the colors summarized inthe Table 3 below resulted:

TABLE 3 Benzyl Alcohol Derivate Color Benzyl alcohol pink Vanillylalcohol red Isovanillyl alcohol yellow-orange p-Hydroxybenzyl alcoholorange

Example 10

Color Intensities as a Function of the Concentration of1,2,3,3-tetramethyl-3H-indolium hydrogen sulfates and of the substitutedbenzyl alcohol

The color reaction was carried out, as in Example 9, at room temperaturein a potassium phosphate system with horse liver alcohol dehydrogenase(10 units/mL), NAD+, 1,2,3,3,-tetramethyl-3H-indolium hydrogen sulfateand substituted benzyl alcohol being used in equimolar amounts, whichvaried from 2 to 10 mmoles/L. The color intensity obtained wasproportional to the concentration used, a concentration of 10 mmoles/Lgiving more intensive colorations than a concentration of 2 mmoles/L.

Example 11

Hair Dyeing

Dyeing solutions were prepared as in Examples 1 to 4. However, insteadof the galactose oxidase, 400 units of horse liver alcoholdehydrogenase, from which the ammonium ions had been removed bydialysis, were used. Subsequently, the hair was dyed as described inExamples 1 to 4.

The color results are summarized in the following Table.

TABLE 4 Benzyl Alcohol Derivative Color Vanillyl alcohol red Isovanillylalcohol yellow p-Hydroxybenzyl alcohol orange p-Aminobenzyl alcohol pink

In the present application, all enzyme concentrations are reported in“units” of the international measured variable, which is recommended bythe International Union For Biochemistry as the standard for all typesof enzymes.

Unless stated otherwise, all percentages are percentages by weight.

What is claimed is:
 1. An agent for dyeing keratin fibers, said agentcontaining at least one compound with a nucleophilic reaction center, atleast one aryl alcohol and at least one oxidizing enzyme; wherein saidat least one compound with said nucleophilic reaction center reacts withsaid at least one aryl alcohol and said at least one oxidizing enzyme toform a dye for the keratin fibers; wherein the at least one compoundwith the nucleophilic reaction center is selected from the groupconsisting of 1,3,3-trimethyl-2-methylene-indoline,1,3,3,4-tetramethyl-2-methylene-indoline,1,3,3,5-tetramethyl-2-methylene-indoline,1,3,3,6-tetramethyl-2-methylene-indoline,1,3,3,7-tetramethyl-2-methylene-indoline,1,3,3,6,7-pentamethyl-2-methylene-indoline,1,3,3,5,7-pentamethyl-2-methylene-indoline,1,3,3,4,7-pentamethyl-2-methylene-indoline,5-chloro-1,3,3-trimethyl-2-methylene-indoline,5-fluoro-1,3,3-trimethyl-2-methylene-indoline,5-isopropyl-1,3,3-trimethyl-2-methylene-indoline,5-hydroxy-1,3,3-trimethyl-2-methylene-indoline, 5-methoxy-1,3,3-trimethyl-2-methylene-indoline, 5-amino- 1,3,3-trimethyl-2-methylene-indoline,5-nitro-1,3,3-trimethyl-2-methylene-indoline,5-N-acetylamino-1,3,3-trimethyl-2-methylene-indoline, 6-hydroxy-1,3,3-trimethyl-2-methylene-indoline,6-methoxy-1,3,3-trimethyl-2-methylene-indoline,5-methoxy-6-nitro-1,3,3-trimethyl-2-methylene-indoline,5-methoxy-6-N-acetylamino-1,3,3-trimethyl-2-methylene-indoline,5-methoxy-6-amino-1,3,3-trimethyl-2-methylene-indoline,5,6-methylenedloxy-1,3,3-trimethyl-2-methylene-indoline,5,6-dihydroxy-1,3,3-trimethyl-2-methylene-indoline,5,6-dimethoxy-1,3,3-trimethyl-2-methylene-indoline,4,5-dihydroxy-1,3,3-trimethyl-2-methylene-indoline,5,7-dihydroxy-1,3,3-trimethyl-2-methylene-indoline,5-amino-6-methoxy-1,3,3-trimethyl-2-methylene-indoline,5-amino-7-hydroxy-1,3,3-trimethyl-2-methylene-indoline,5-hydroxy-7-amino-1,3,3-trimethyl-2-methylene-indoline,5-hydroxy-7-N-acetylamino-1,3,3-trimethyl-2-methylene-indoline.1-methyl-3-spiro-cyclopropyl-2-methylene-indoline,1-methyl-3-spiro-cyclohexyl-2-methylene-indoline,1-methyl-3spiro-cyclohexyl-5-hydroxy-2-methylene-indoline,1methyl-3spirocyclohexyl-5-hydroxy-2-methylene-indoline,1-(2′-hydroxyethyl)-3,3-dimethyl-2-methylene-indoline,1,3,3-trimethyl-2-methylene-3H-benzindole andN-ethyl-2-methylene-benzthiazole; or a salt thereof.
 2. The agent asdefined in claim 1, wherein said at least one aryl alcohol is selectedfrom the group consisting of benzyl alcohol, 4-hydroxy-benzyl alcohol,4-hydroxy-3-methoxybenzyl alcohol, 3-hydroxy-4-methoxy-benzyl alcohol,3,5-dimethoxy-4hydroxybenzyl alcohol, 3,4-dihydroxybenzyl alcohol,2-hydroxy-3-methoxybenzyl alcohol, 4-ethoxybenzyl alcohol,4-carboxy-benzyl alcohol, 2,5-dihydroxybenzyl alcohol,2,4-dihydroxy-benzyl alcohol, 2-hydroxybenzyl alcohol,3,5-dimethoxy-4-hydroxybenzyl alcohol, 4-hydroxy-2-methoxybenzylalcohol, 2,4-dimethoxybenzyl alcohol, 2,3-dimethoxybenzyl alcohol,2,5-dimethoxybenzyl alcohol, 3,5-dimethoxybenzyl alcohol,3,4-methylene-dioxybenzyl alcohol, 3,4-dimethoxybenzyl alcohol,3-ethoxy-4-hydroxybenzyl alcohol, 3,5-dimethyl-4-hydroxybenzyl alcohol,3,4-dimethoxy-5-hydroxybenzyl alcohol, 3,4,5-trimethoxybenzyl alcohol,2,4,6-trihydroxybenzyl alcohol, 3,4,5-trihydroxybenzyl alcohol,2,3,4-tri-hydroxybenzyl alcohol, 3,5-di-t-butyl-4-hydroxybenzyl alcohol,2-nitrobenzyl alcohol, 3-nitrobenzyl alcohol, 4-nitrobenzyl alcohol,2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 3-amino-4-methylbenzylalcohol, 3,5-diaminobenzyl alcohol, 4-aminobenzyl alcohol,4-dimethylamino-benzyl alcohol, 4-diethylamino-2-hydroxybenzyl alcohol,4-diethylamino-3-methoxybenzyl alcohol, 4-dimethylamino-2-methoxybenzylalcohol, 4-dibutylaminobenzyl alcohol,3-methoxy-4-(1-pyrrolidinyl)-benzyl alcohol,(4-methoxy-naphthalene-1-yl)-methanol,(4-dimethylamino-naphthalene-1-yl)-methanol,2-(hydroxymethyl)-1-naphthol, 1-naphthalene-methanol,2-naphthalene-methanol, (2-methoxy-naphthalene-1-yl)-methanol,4-hydroxy-methyl-naphthalene-1-ol, 4′-hydroxy-methyl-biphenyl-4-ol,(4-hydroxymethyl-phenyl)-methanol,4-(3-hydroxy-propenyl)-2-methoxyphenol,4-(3-hydroxy-propenyl)-2,6,-dimethoxyphenol,3-(4-dimethylaminophenyl)-prop-2-ene-1-ol,5-(4-(diethylaminophenyl)-penta-2,4-diene-1-ol, thiophene-2-yl-methanol,(5-hydroxymethylthiophene-2-yl)-methanol, thiophene-3-yl-methanol,(1H-pyrrole-2-yl)-methanol, (1-methyl-1H-pyrrole-2-yl)-methanol,(5-methylfuran-2-yl)-methanol, (1H-indole-3-yl)-methanol, and(6-methyl-1H-indole-3-yl)-methanol.
 3. The agent as defined in claim 1,wherein, the at least one oxidizing enzyme is selected from the groupconsisting of alcohol dehydrogenases, alcohol oxidases, flavin oxidases,laccases, peroxidases, hydroxylases and mono-oxygenases.
 4. The agent asdefined in claim 1, wherein said at least one oxidizing enzyme isselected from the group consisting of vanillyl oxidase, derivatives ofvanillyl oxidase and derivatives of galactose oxidase.
 5. An agent fordyeing keratin fibers in the form of a 2-component kit, comprising acomponent (A) and a component (B) separate from said component (A);wherein said component (A) contains a compound with a nucleophilicreaction center, an aryl alcohol and optionally a nicotinamide co-factorand a butter, and said component (B) contains an oxidizing enzyme andoptionally the nicotinamide co-factor and the buffer; and wherein saidcompound with said nucleophilic reaction center reacts with said alcoholand said oxidizing enzyme to form a dye for the keratin fibers; andwherein said compound with said nucleophilic reaction center is selectedfrom the group consisting of 1,3,3-trimethyl-2-methylene-indoline,1,3,3,4-tetramethyl-2-methylene-indoline,1,3,3,5-tetramethyl-2-methylene-indoline,1,3,3,6-tetramethyl-2-methylene-indoline,1,3,3,7-tetramethyl-2-methylene-indoline,1,3,3,6,7-pentamethyl-2-methylene-indoline,1,3,5,7-pentamethyl-2-methylene-indoline,1,3,3,4,7-pentamethyl-2-methylene-indoline,5-chloro-1,3,3-trimethyl-2-methylene-indoline,5-fluoro-1,3,3-trimethyl-2-methylene-indoline,5-isopropyl-1,3,3-trimethyl-2-methylene-indoline,5-hydroxy-1,3,3-trimethyl-2-methylene-indoline,5-methoxy-1,3,3-trimethyl-2-methylene-indoline,5-amino-1,3,3-trimethyl-2-methylene-indoline.5-nitro-1,3,3trimethyl-2-methylene-indoline.5-N-acetylamino-1,3,3-trimethyl-2-methylene-indoline,6-hydroxy-1,3,3-trimethyl-2-methylene-indoline,6-methoxy-1,3,3-trimethyl-2-methylene-indoline,5methoxy-6-nitro-1,3,3-trimethyl-2-methylene-indoline,5-methoxy-6-N-acetylamino-1,3,3-trimethyl-2-methylene-indoline,5-methoxy-6-amino-1,3,3-trimethyl-2-methylene-indoline,5,6-methylenedioxy-1,3,3-trimethyl-2-methylene-indoline,5,6-dihydroxy-1,3,3-trimethyl-2-methylene-indoline,5,6-dimethoxy-1,3,3-trimethyl-2-methylene-indoline,4,5-dihydroxy-1,3,3-trimethyl-2-methylene-indoline,5,7-dihydroxy-1,3,3-trimethyl-2-methylene-indoline,5-amino-6-methoxy-1,3,3-trimethyl-2-methylene-indoline,5-amino-7-hydroxy-1,3,3-trimethyl-2-methylene-indoline,5-hydroxy-7-amino-1,3,3-trimethyl-2-methylene-indoline,5-hydroxy-7-N-acetylamino-1,3,3-trimethyl-2-methylene-indoline,1-methyl-3-spiro-cyclopropyl-2-methylene-indoline,1-methyl-3-spiro-cyclohexyl-2-methylene-indoline,1-methyl-3-spiro-cyclohexyl-5-hydroxy-2-methylene-indoline,1-methyl-3-spirocyclohexyl-5-methoxy-2-methylene-indoline,1-(2′-hydroxyethyl)-3,3-dimethyl-2-methylene-indoline,1,3,3-trimethyl-2-methylene-3H-benzindole andN-ethyl-2-methylene-benzthiazole; or a salt thereof.
 6. An agent fordyeing keratin fibers in the form of a 2-component kit, comprising acomponent (A) and a component (B) separate from said component (A);wherein said component (A) contains a compound with a nucleophilicreaction center, an aryl alcohol, an oxidizing enzyme and optionally anicotinamide co-factor and a buffer, and said component (B) containssaid alcohol and optionally the nicotinamide co-factor and the buffer;and wherein said compound with said nucleophilic reaction center reactswith said alcohol and said oxidizing enzyme to form a dye for thekeratin fibers; and wherein said compound with said nucleophilicreaction center is selected from the group consisting of1,3,3-trimethyl-2-methylene-indoline,1,3,3,4-tetramethyl-2-methylene-indoline, 1,3,3,5-tetramethyl-2-methylene-indoline, 1,3,3,6-tetramethyl-2-methylene-indoline,1,3,3,7-tetramethyl-2-methylene-indoline,1,3,3,6,7-pentamethyl-2-methylene-indoline,1,3,3,5,7-pentamethyl-2-methylene-indoline,1,3,3,4,7-pentamethyl-2-methylene-indoline,5-chloro-1,3,3-trimethyl-2-methylene-indoline,5-fluoro-1,3,3-trimethyl-2-methylene-indoline,5-isopropyl-1,3,3-trimethyl-2methylene-indoline,5-hydroxy-1,3,3-trimethyl-2-methylene-indoline,5-methoxy-1,3,3-trimethyl-2-methylene-indoline, 5-amino-1,3,3-trimethyl-2-methylene-indoline,5-nitro-1,3,3-trimethyl-2-methylene-indoline,5-N-acetylamino-1,3,3-trimethyl-2-methylene-indoline,6-hydroxy-1,3,3-trimethyl-2-methylene-indoline,6-methoxy-1,3,3-trimethyl-2-methylene-indoline,5-methoxy-6-nitro-1,3,3-trimethyl-2-methylene-indoline,5-methoxy-6-N-acetylamino-1,3,3-trimethyl-2-methylene-indoline,5-methoxy-6-amino-1,3,3-trimethyl-2-methylene-indoline,5-methylenedloxy-1,3,3-trimethyl-2-methylene-indoline,5,6-dihydroxy-1,3,3-trimethyl-2-methylene-indoline,5,6-dimethoxy-1,3,3-trimethyl-2-methylene-indoline,4,5-dihydroxy-1,3,3-trimethyl-2-methylene-indoline,5,7-dihydroxy-1,3,3-trimethyl-2-methylene-indoline,5-amino-6-methoxy-1,3,3-trimethyl-2-methylene-indoline,5-amino-7-hydroxy-1,3,3-trimethyl-2-methylene-indoline,5-hydroxy-7-amino-1,3,3-trimethyl-2-methylene-indoline,5-hydroxy-7-N-acetylamino-1,3,3-trimethyl-2-methylene-indoline,1-methyl-3-spiro-cyclopropyl-2-methylene-indoline,1-methyl-3-spiro-cyclohexyl-2-methylene-indoline,1-methyl-3-spiro-cyclohexyl-5-hydroxy-2-methylene-indoline,1-methyl-3-spirocyclohexyl-5-methoxy-2-methylene-indoline,1-(2′-hydroxyethyl)-3,3-dimethyl-2-methylene-indoline,1,3,3-trimethyl-2-methylene-3H-benzindole andN-ethyl-2-methylene-benzthiazole; or a salt thereof.
 7. The agent asdefined in claim 1, consisting of an anhydrous agent and prior to dyeingthe keratin fibers said anhydrous agent is mixed with water or anaqueous preparation containing cosmetic additive ingredients.
 8. Amethod of dyeing keratin fibers, said method comprising the steps of: a)providing an agent for dyeing keratin fibers containing at least onecompound with a nucleophilic reaction center, at least one aryl alcoholand at least one oxidizing enzyme, wherein said at least one compoundwith said nucleophilic reaction center reacts with said at least onearyl alcohol and said at least one oxidizing enzyme to form a dye forthe keratin fibers; b) applying said agent to keratin fibers to be dyed;and c) after the applying of step b), allowing said agent to act on saidkeratin fibers for from 10 to 45 minutes at a temperature of 15° C. to50° C.; and d) after the allowing of step c), rinsing said keratinfibers and subsequently drying; and wherein said at least one compoundwith said nucleophilic reaction center is selected from the groupconsisting of 1,3,3-trimethyl-2-methylene-indoline,1,3,3,4-tetramethyl-2-methylene-indoline,1,3,3,5-tetramethyl-2-methylene-indoline,1,3,3,6-tetramethyl-2-methylene-indoline,1,3,3,7-tetramethyl-2-methylene-indoline,1,3,3,6,7-pentamethyl-2-methylene-indoline,1,3,3,5,7-pentamethyl-2-methylene-indoline,1,3,3,4,7-pentamethyl-2-methylene-indoline,5-chloro-1,3,3-trimethyl-2-methylene-indoline,5-fluoro-1,3,3-trimethyl-2-methylene-indoline,5-isopropyl-1,3,3-trimethyl-2-methylene-indoline, 5-hydroxy-1,3,3-trimethyl-2-methylene-indoline,5-methoxy-1,3,3-trimethyl2-methylene-indoline,5-amino-1,3,3-trimethyl-2-methylene-indoline,5-nitro-1,3,3-trimethyl-2-methylene-indoline,5-N-acetylamino-1,3,3-trimethyl-2-methylene-indoline,6-hydroxy-1,3,3-trimethyl-2-methylene-indoline,6-methoxy-1,3,3-trimethyl-2-methylene-indoline,5-methoxy-6-nitro-1,3,3-trimethyl-2-methylene-indoline,5-methoxy-6-N-acetylamino-1,3,3-trimethyl-2-methylene-indoline,5-methoxy-6-amino-1,3,3-trimethyl-2-methylene-indoline,5,6-methylenedloxy-1,3,3-trimethyl-2-methylene-indoline,5,6-dihydroxy-1,3,3-trimethyl-2-methylene-indoline,5,6-dimethoxy-1,3,3-trimethyl-2-methylene-indoline,4,5-dihydroxy-1,3,3-trimethyl-2-methylene-indoline,5,7-dihydroxy-1,3,3-trimethyl-2-methylene-indoline,5-amino-6-methoxy-1,3,3-trimethyl-2-methylene-indoline,5-amino-7-hydroxy-1,3,3-trimethyl-2-methylene-indoline.5-hydroxy-7-amino-1,3,3-trimethyl-2-methylene-indoline,5-hydroxy-7-N-acetylamino-1,3,3-trimethyl-2-methylene-indoline,1-methyl-3-spiro-cyclopropyl-2-methylene-indoline,1-methyl-3-spiro-cyclohexyl-2-methylene-indoline,1-methyl-3-spiro-cyclohexyl-5-hydroxy-2-methylene-indoline,1-methyl-3-spirocyclohexyl-5-methoxy-2-methylene-indoline,1-(2′-hydroxyethyl)-3,3-dimethyl-2-methylene-indoline,1,3,3-trimethyl-2-methylene-3H-benzindole andN-ethyl-2-methylene-benzthiazole; or a salt thereof.
 9. The agent asdefined in claim 1, wherein said aryl alcohols are each of formula (I):Ar—(CH═CH)_(n)—CH₂OH  (I), wherein n=0, 1 or 2 and Ar is a group havingone of the following formulae:

wherein Y is an oxygen atom, a sulfur atom or a NR^(a) group; R1′, R2′,R3′, R4′, R5′, R6′ and R7′, independently of one another, are each ahydrogen atom, a hydroxy group, a methoxy group, an aryl group, ahalogen atom, a —CHO group, a —COR^(a) group, a —CO₂R^(a) group, anNO₂-group, an —OCOR^(a) group, an —OCH₂-aryl group, an —NH₂ group, an—NH₃ ³⁰ group, an —NHR^(a) group, an —NH₂R^(a) group, an —N(R^(a))₂group, an —N(R^(a))₃ ⁺ group, an —NHCOR^(a) group, an —NHCOOR^(a) group,in which R^(a) is a hydrogen atom, a linear or branched C1 to C4 alkylgroup, an optionally substituted, aromatic, carbocyclic group orheterocyclic group, or R4′ and R5′ together with a carbon atom of anaromatic ring of said Ar form a 5-member or 6-member alicyclic oraromatic ring, which optionally may contain one or more sulfur, nitrogenor oxygen atoms.